Unit 5 Organic Chemistry

Reactions
Benzene
Combustion

In excess air, benzene burns to form carbon dioxide and water.

1
C6 H 6 +7 O 2 6 C O2 +3 H 2 O
2

In limited air, it burns with a smoky flame forming carbon and water.

1
C6 H 6 +1 O2 6 C +3 H 2 O
2

Free-Radical Addition

Chlorine bubble chlorine into boiling benzene in the presence of

ultraviolet light, and addition takes place. The chlorine radicals add on,
one at a time to the benzene ring until all the -bonds have been broken.
(Bromine acts similarly)

Hydrogen when heated with a Nickel catalyst, hydrogen adds on and

cyclohexane is formed.

Electrophilic Substitution

Mechanism given that and electrophile E+ adds on to a carbon atom on

the benzene ring:
 Nitration - when concentrated nitric acid, and a catalyst of concentrated
sulphuric acid are warmed together at 60 degrees under reflux,
nitrobenzene and water are formed. The electrophile is the NO 2 group,
which is formed by a protonated nitric acid molecule. (below 55 degrees,
the reaction is too slow, above 65 degrees, a second nitrogen dioxide
group Is substituted onto the ring.)

Halogens with a catalyst of anhydrous iron halide, chlorine and bromine

react rapidly with benzene, if the reagents are dry. For the bromination of
benzene, the catalyst is made in situ by adding iron filings to a mixture of
benzene and liquid bromine:

2 Fe+ 3 B r 2 2 FeB r 3

This can then react with more bromine to form the electrophile:

+

++ FeB r 4

FeBr 3+ B r 2 B r

Friedel-Crafts, Alkylation benzene reacts with a halogenoalkane in the

presence of a catalyst anhydrous aluminium chloride, in dry conditions to
form a hydrocarbon and gaseous hydrogen halide:
 Friedel-Crafts, Acylation benzene reacts with an acid chloride with the
catalyst anhydrous aluminium chloride, which produces the electrophile
CH3C+=O:

Sulfonation benzene reacts with fuming sulphuric acid at 40 degrees

under reflux. The electrophile is the SO 3. The products are benzesulphonic
acid and water:

Alkenes benzene adds onto alkenes to form a branched chain alkane

substituted into the benzene ring (except with ethene, as it has too few
carbons)
Detergents add a long chain alkene and benzene, then sulphonate the
product, then neutralise with sodium hydroxide to form a detergent. It
makes an excellent detergent as its calcium salt is soluble, so no scum if
formed in hard water.

Phenol
Electrophilic Aromatic Substitution reactions

Bromine bromine water and phenol and water react, going from the red-
brown bromine colour, and forming a white antiseptic smelling precipitate
of 2,4,6-tribomophenol

The electrophile is the + bromine atom in an HOBr molecule, formed

form the reaction of bromine and water
 B r 2+ H 2 O HOBr+ HBr

Nitration reacts with dilute nitric acid to form 2-nitrophenol and 4-

nitrophenol plus water

Reacts with concentrated nitric acid, more nitro groups substitute to give
2,4,6-trinitrophenol

Phenol as an acid

Water forms the phenate ion:

+ +C6 H 5 O
C6 H 5 OH + H 2 O H 3 O

Sodium hydroxide reacts in a neutralisation reaction to form the salt

sodium phenate and water

Sodium- reacts with metallic sodium to form hydrogen and the salt sodium
phenate
 Sodium hydrogencarbonate/ sodium carbonate phenol is a weaker acid
than carbonic acid, so it does not liberate carbon dioxide from either
sodium hydrogen carbonate or sodium carbonate.

Phenol as an alcohol

Acid chlorides, aliphatic reacts slowly to form an ester and fumes of

hydrogen chloride. The oxygen atom in phenol acts as a nucleophile and
attacks the + carbon atom on the acid chloride.
Acid chlorides, aromatic reacts in aqueous solution to create C 6H5O- ions,
which are a stronger nucleophile than phenol molecules.

Benzoic Acid
When warmed with concentrated nitric and sulphuric acids, 3-nitrobenzoic
acid and water are formed.

2-methlynitrobenzene
Preparation

Add the nitrating mixture, consisting of concentrated nitric and sulphuric

acids, and mix with benzene, then heat in a water bath at 50 degrees.
After refluxing, the mixture is cooled and water added to dilute the acids.
The mixture is then poured into a separating funnel and the bottom layer,
which contains the methylnitrobenzenes is run off.
This impure mixture is washed with sodium carbonate solution, to remove
residual acid, then with water to remove any residiual sodium carbonate in
a separating funnel.
It is dried by adding lumps of anhydrous calcium chloride and leaving for
several hours
It is then decanted into a flask and distilled. The fraction that boils
between 218 and 222 degrees is collected. This is 2-methlybenzene.

Amines
Preparation

Reaction of ammonia with a halogenoalkane. If a halogenoalkane is mixed

with excess concentrated ammonia in aqueous ethanolic solution, a
primary amine is obtained.
 An excess of the halogenoalkane will yield the secondary amine.

Reduction of a nitrile/amide reduced by LiAlH 4 in dry ether, then

hydrolysis of the adduct with dilute acid

As a Base

Water they react reversibly, forming OH- ions

Acids when reacted with an acid, a salt is formed.

With Acid Chlorides

A lone pair of electrons on the nitrogen in the amine acts as a nucleophile

and attacks the + carbon in the in acid chloride in an addition-elimination
reaction

With Halogenoalkanes

A primary amine reacts with a halogenoalkane to produce a mixture of the

salts of secondary and tertiary amines. The reagents are heated in
ethanolic solution in a sealed tube

If the free amine is required, a strong base is added to the solution and
any unreacted primary amine, and secondary and tertiary amines are
formed

With d-block metal ions

Amines can act as ligands; the lone pair of electrons on the amine group
can form a bond with the empty orbital of some d-block metal ions. The
 reaction is similar to the formation of ammines with excess ammonia. (see
transition metals for more details)

Phenylamine
Preparation

Nitrobenzene and tin mixed in a round bottomed flask with a reflux

condenser. Concentrated hydrochloric acid is carefully added, and after
the rapid evolution of hydrogen has ceased, the mixture is heated to 100
degrees in a bath of boiling water for 30 minutes. This is the half equation
for the reduction of the phenylamine and the phenylammonium ion is
formed. The lone pair on the phenylamine picks up a hydrogen ion from
the acid:

The tin (Sn) acts as a catalyst. It is oxidised to provides the electrons used
to reduce the nitrobenzene in the presence of the acid.

To remove the extra hydrogen from the NH3 group, sodium hydroxide
solution is added in excess:

Finally, the mixture is steam distilled by blowing steam onto the mixture
and condensing the phenylamine, which is then placed in a separating
funnel with sodium chloride to reduce the solubility and the phenylamine
layer is run off and dried with potassium carbonate to remove water. It is
then distilled using an air condenser.
A summary reaction can be represented as:

Electrophilic substitution Reactions

 Bromination phenylamine and bromine water form a white precipitatie of
2,4,6-tribromophenylamine and hydrogen bromide:

Reactions of the NH 2 group

It acts a weak base, so reacts reversibly with water. It is a weaker base

than aliphatic amines.
Acid chloride - Reacts with, like an aliphatic primary amine, an acid
chloride to form a secondary amine. The phenylamine acts as a
nucleophile

Nitrous acid nitrous acid is unstable, and has to be made is situ by

mixing a solution of sodium nitrate, NaNO2 with excess dilute hydrochloric
acid.

This reacts with the phenylamine to form benzenediazonium chloride in an

exothermic reaction. The temperature must be maintained between 0 and
10 degrees. The ionic equation is:

Benzenediazonium Compounds
Preparation

Nitrous acid and phenylamine between 0 and 10 degrees.

Coupling reactions

Phenol phenol mixed with sodium hydroxide, to give the phenate ion:
 This is then attacked by a diazonium ion by electrophilic substitution to
form a yellow precipitate of 4-hydroxyazobenzene:

2-napthol napthols are compounds with two fused benzene rings and an
OH group on one of the rings. It couples with diazonium ions to form a red
precipitate, under the same conditions as phenol, dissolved in sodium
hydroxide:

Phenylamine with vigorous shaking, a yellow precipitate is formed:

Amides
Preparation

Ammonia and an acid chloride

Hydrolysis

When boiled under reflux with either aqueous acid or alkali, amides are
hydrolysed. E.g. ethanamide hydrolysed with dilute acid:

Polyamides

Condensation polymerisation formed from two different monomers, each

with two identical functional groups, or in some cases, a single monomer
that has two different functional groups:

e.g. Kevlar:
 e.g. Nylon:
Addition Polymerisation a polymer formed from monomers containing a
C=C group. The bond in the monomer breaks, and a new bond forms
with another monomer. As a bond is weaker than a bond, and as all
bond making is exothermic, such polymerisation is exothermic.

E.g. poly(propenamide)

E.g poly(ethanol) the monomer does not exist. The

polymer is manufactured by reacting the polymer polyvinylacetate with
methanol in a transesterification reaction.